Most of the economically significant base metal ore deposits worldwide contain mixed sulfides. The conventional methods for beneficiation of such ores involve, initially, bulk flotation of metal sulfides and/or subsequent selective flotation of each metal sulfide, depending on individual ore characteristics. Oxidized sulfides are normally recovered separately from nonoxidized sulfides ("consecutive flotation"), since they are not readily floatable except after pretreatment with sulfidizers, to render their surfaces hydrophobic. After such pretreatment, the oxidized sulfides may also be recovered by flotation.
Conventional selective flotation of mineral sulfide particles requires grinding of the ore to liberation size, formation of an ore pulp, addition of appropriate depressors, activators, collectors and frothing agents and subsequent flotation in multiple stages.
Pyrites are some of the most common constituents of base metal ores. Their presence in flotation is undesirable because they are generally difficult to depress and normally require a relatively highly alkaline medium. Consequently, a great number of industrial scale flotation separations are performed at an alkaline pH obtained by addition of pH modifiers to the pulp, such as lime, soda ash etc. (hereinafter referred to as "alkaline flotation"). Unfortunately, alkaline flotation results in consumption of substantial quantities of such modifiers, and often in consumption of corresponding amounts of pH neutralizers downstream. In addition, high alkalinity often causes overdepression of other valuable components and decreases the efficiency and selectivity of the separation, requiring larger amounts of activators and collectors, and resulting in increased processing costs.
As a result of the widespread use of highly alkaline flotation media, the flotation behavior of sulfides in such media has been the subject of extensive study which has generated voluminous literature directed to both the theoretical and practical aspects of such flotation. For an overview of the research published on this topic, see Leja, J. (1982), Surface Chemistry of Froth Flotation, pp. 642-659, Plenum Press, New York; and Staff (1982), Flotation Review, Mining Engr., Vol. 34, Nos. 3, 4, pp. 275-279, 377-381. However, comparatively little investigation has been devoted to sulfide flotation in the absence of pH modifiers, i.e., at a natural (unmodified) pH determined mainly by the particular ore composition and the quality of the water supply available.
Soluble cyanides (such as sodium and potassium) and soluble sulfides such as sodium sulfide, hydrogen sulfide, polysulfides, etc., are commonly used in alkaline flotation as follows: cyanides are used as complexing and depressing agents; soluble sulfides are used (a) as sulfidizers for oxides and oxidized sulfides (in "consecutive" flotation of oxides); (b) as sulfide depressants (after bulk flotation and/or prior to selective flotation); and (c) as collector desorbents subsequent to the collection of a floated fraction. If Na.sub.2 S is used, the quantity required for all of the above uses is of the order of 1,000 g/ton of ore or more.
Dilute solutions of sodium sulfide (i.e., of the order of 0.1M) have been used historically by investigators to pretreat mineral surfaces preparatory to microflotation studies, in order to displace elemental sulfur and other surface oxidation products from sulfide minerals and thereby carefully control experimental conditions, as is necessary in basic research. Such surfaces are thoroughly washed, however, prior to actually carrying out the microflotation tests.
One such basic research study was conducted by Y. Nakahiro: Effect of Sodium Sulfide on the Prevention of Copper Activation for Sphalerite, Mem. Fac. Engr. Kyoto Univ., Part 4, Oct. 1978; pp. 241-257. It involved only the investigation of the effect of sodium sulfide and/or sodium cyanide specifically on the copper activation of sphalerite. The sample tested involved extremely pure copper/zinc sulfide from high grade samples further treated to eliminate quartz, galena, pyrite and other impurities. The results indicated that, in that carefully controlled sample and system, small amounts of Na.sub.2 S had a depressant effect on sphalerite, which was enhanced by the copper ion complexing action of NaCN. However, this effect was pH dependent, the author recommending separation of copper from zinc at an alkaline pH above 8.1. Thus, Nakahiro's study was of limited scope and applicability and its results spoke in favor of pH modification to improve selective flotation.
U.S. Pat. No. 1,469,042 to Hellstrand, issued on Sept. 25, 1923, is directed to a process of bulk (not selective) flotation of a lead-iron (or lead-iron-copper) concentrate using 1-7 lbs of Na.sub.2 s per ton of mill feed during the wet-grinding stage to accelerate flotation of (i.e., activate, not depress) the constituents of said concentrate and inhibit that of zinc. Therefore, this is not a process of true selective flotation, which involves flotation of one metalliferous constituent at a time and removal thereof before flotation of another metalliferous constituent. In addition, amounts of Na.sub.2 S used are much higher than in the process of the present invention, and Hellstrand's process is not applied to oxidized sulfides (non-simultaneous, i.e., sequential flotation), the term "flotation of mixed sulfides", as used in this patent, meaning simply flotation of sulfides of several metals, i.e., what is today known in the industry as a bulk concentrate.
U.S. Pat. No. 1,916,196 to Ayer, issued on July, 4, 1933, is directed to a process for simultaneous flotation of mixed copper sulfides (sulfides, oxidized sulfides, and carbonates) using soluble sulfides, such as Na.sub.2 S, as conditioning additives together with other sulfidizing agents at a carefully controlled pH range between 4.8 and 6.5, the objectives being enhancement of sulfidization, precipitation of copper ions from solution and recovery thereof as sulfides, and bulk flotation of all metalliferous mineral particles.
A method was sought which would decrease the cost and/or increase the efficiency of selective base metal ore flotation, particularly one which avoids the need for making a large capital expenditure, such as building of new facilities or extensive modification of existing ones. Accordingly, a method was sought which would decrease the number of flotation stages, reduce reagent consumption, and increase flotation selectivity.